Cellulose composite materials and methods of making and using the same

Abstract

The present disclosure provides a composite of (a) oxidized cellulose comprising at least one carboxyl and (b) at least one component selected from a diamine, a diol, or mixture thereof. This disclosure further relates to methods of making such composite materials and suitable uses thereof, including in fibers, fabrics, textiles, films, fillers, packaging materials, plastics, etc.

We claim: 
     
       1. A method of making a composite comprising mixing an oxidized cellulose comprising at least one carboxyl with at least one component selected from a diamine, a diol, or mixture thereof to form a composite, wherein the oxidized cellulose is formed by a method comprising at least one step comprising oxidation with hydrogen peroxide and a catalyst comprising iron, copper, or a combination of iron and copper at an acidic pH. 
     
     
       2. The method of  claim 1 , wherein the oxidized cellulose comprises a carboxyl content of from about 1 meq/100 g to about 15 meq/100 g. 
     
     
       3. The method of  claim 1 , wherein the oxidized cellulose comprises both carboxyl and aldehyde groups, and wherein the ratio of carboxyl content to aldehyde content is from about 1:1 to about 3:1. 
     
     
       4. The method of  claim 1 , wherein the oxidized cellulose comprising at least one carboxyl is reacted with at least one diamine selected from at least one of tetramethylenediamine, hexamethylenediamine, nonamethylenediamine, decamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4(2,4,4)-trimethylhexamethylenediamine, 5-methylnonamethylenediamine, 2,4-dimethyloctamethylenediamine, metaxylylenediamine, paraxylylenediamine, 1,3-bis(aminomethyl)cyclohexane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, 3,8-bis(aminomethyl)tricyclodecane, bis(4-aminocyclohexyl)methane, bis(3-methyl-4-aminocyclohexyl)methane, 2,2-bis(4-aminocyclohexyl)propane, bis(aminopropyl)piperazine, aminoethylpiperazine, and mixtures thereof. 
     
     
       5. The method of  claim 4 , wherein the oxidized cellulose comprising at least one carboxyl is reacted with hexamethylenediamine. 
     
     
       6. The method of  claim 1 , wherein the oxidized cellulose comprising at least one carboxyl is reacted with at least one diol selected from at least one of ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butane diol, 1,2-butylene diol, 1,4-butylene diol, cyclohexane dimethanol, neopentyl glycol, glycerol, and mixtures thereof. 
     
     
       7. The method of  claim 6 , wherein the oxidized cellulose comprising at least one carboxyl is reacted with ethane-1,2-diol. 
     
     
       8. The method of  claim 6 , wherein the oxidized cellulose comprising at least one carboxyl is reacted with 1,4-butane diol. 
     
     
       9. The method of  claim 1 , wherein the reaction further comprises at least one dicarboxylic acid component selected from the group consisting of adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, phthalic anhydride terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, hept-5-ene-2,3-dicarboxylic acid, 5-sodiumsulfoisophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, diglycolic acid, and mixtures thereof. 
     
     
       10. The method of  claim 1 , wherein the oxidized cellulose is formed by a method comprising at least one step comprising catalytic oxidation with iron and hydrogen peroxide at an acidic pH. 
     
     
       11. The method of  claim 1 , wherein the oxidized cellulose is further treated with at least one carboxylating treatment following the at least one oxidation step. 
     
     
       12. The method of  claim 11 , wherein the carboxylating treatment comprises application of chlorine dioxide and hydrogen peroxide to the oxidized cellulose. 
     
     
       13. The method of  claim 11 , wherein the at least one catalytic oxidation and the at least one carboxylating treatment take place during a multi-stage bleaching process, and wherein the multi-stage bleaching process is a five stage bleaching process comprising a sequence chosen from (C/A)(OX)(C/A)E 2 D 2 , (C/A)(OX)D 1 E 2 (C/A), (C/A)(OX)(C/A)E 2 (C/A), (C/A)E 1 D 1 (OX)(C/A), D 0 E 1 (C/A)(OX)(C/A), (C/A)E 1 (C/A)(OX)(C/A), (C/A)(OX)(C/A)(OX)D 2 , (C/A)(OX)D 1 (OX)(C/A), Do(OX)(C/A)(OX)(C/A), and (C/A)(OX)(C/A)(OX)(C/A), where OX refers to the catalytic oxidation, C/A refers to the carboxylating treatment, D refers to a chlorine dioxide bleaching stage, and E refers to an E, EO, Ep, or EoP bleaching stage.